Process for producing imidochloride containing compounds by two stage chlorination of secondary amines



United States Patent 3 541,091 PROCESS FOR PROIiUCING IMIDOCHLORIDE CONTAINING COMPOUNDS BY TWO STAGE CHLORINATION OF SECONDARY AMINES Wilfried Zecher, Cologne-Stammheim, and Horst Tarnow and Hans Holtschmidt, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany N0 Drawing. Continuation of application Ser. No. 505,965, Nov. 1, 1965. This application Dec. 28,

1967, Ser. N0. 694,094 Claims priority, application Germany, Dec. 21, 1964, F 44,766 Int. Cl. C07d 93/10 US. Cl. 260243 4 Claims ABSTRACT OF THE DISCLOSURE A process for producing compounds containing an imidochloride group which comprises chlorinating a secondary amine in two stages; the first at a temperature of -20 to +60 C. until all easily replaceable hydrogen atoms are replaced by chlorine and then continuing the chlorination at 70 to 250 C. to produce the desired compound.

This application is a continuation of application Ser. No. 505,965, filed Nov. 1, 1965, now abandoned.

Chlorination of acylamines and also of tertiary amines is known and results in compounds the common characteristics of which is the imidochloride grouping (Angewandte Chemie, 74, 848 (1962)).

It has now been found that chlorine-containing organic nitrogen compounds which have from 1 to 4 imidochloride groupings are obtained, when secondary amines of the formula /R2 R1-- -C\Ra] LH H n for the hydrochlorides of such amines are chlorinated in a stepwise chlorination, optionally under the action of ultraviolet light, the first step being carried out at a temperature between about -20 and about +60 C. until all easily exchangeable hydrogen atoms are substituted by chlorine, continuing the chlorination at a temperature between about 70 to about 250 C. and isolating the resulting imidochlorides of the general formula In the above formulae, the meaning of the symbols is as follows:

R is alkyl having 2 to 6 carbon atoms, aryl (preferably monoor dinuclear), aralkyl (preferably monoor dinuclear with an alkyl group having 1 to 6 carbon atoms) or a 5- to 6-membered heterocyclic radical, having from 1 to 3 nitrogen atoms as an only hetero atom, such heterocyclic ring possibly containing a fused 4- to 6-membered carbocyclic ring system.

The above radicals may be substituted with one or more of the same or different halogen, cyano, alkoxy with 1 to 6 carbon atoms, aroxy (preferably monoor di- 3,541,091 Patented Nov. 17, 1970 R is alkyl having 1 to 6 carbon atoms, aryl (preferably monoor dinuclear), aralkyl (preferably monoor dinuclear with an alkyl group having 1 to 6 carbon atoms) or a 5- to 6-membered heterocyclic radical, having from 1 to 3 nitrogen atoms as an only heteroatom, such heterocyclic ring possibly containing a fused 4- to 6-membered carbocyclic ring system,

R may also stand for halogen, cyano, chyorocarbonyl, hydro carbonyl, alkoxycarbonyl (preferably with 1 to 6 carbon atoms) and alkylamino (alkyl having preferably 1 to 6 carbon atoms),

R is hydrogen or halogen, preferably fluorine, chlorine or bromine,

R is defined as R but containing additional chlorine atoms introduced during the reaction. The total number of chlorine atoms ranges from a complete replacement of all reactable hydrogen atoms to a partial replacement depending on the reaction conditions and the product desired,

R is defined as R respectively but containing additional chlorine atoms introduced during the reaction. The total number of chlorine atoms ranges from a complete replacement of all reactable hydrogen atoms to a partial replacement depending on the reaction conditions and the product desired,

R may also be linked to R via one or more, same or different nitrogen, oxygen, sulphur, methine or methyl ene radicals to form a 5- or 6-membered ring. Normally from 1 to 3 such heterocyclic atoms are preferred. In such a case,

R and R are defined as R and R when so connected but containing additional chlorine atoms ranging from complete replacement of the reactable hydrogen atoms to a partial replacement again depending on the reaction conditions and the desired product.

Examples of substituted and unsubstituted alkyl radicals with a definition of R to R above are the following:

Methyl-, ethyl-, propyl-, isopropyl-, n-butyl-, isobutyl-, n-hexyl-, isoheXyl-, cyclohexyl-, fluoromethyl-, trichlorometthyl-, chloroethyl-, 1,2-dichloroethyl-, 1-bromo-2- chloroethyl-, bromo-ethyl-, B-chloroethyL, ot-fluoroethyL, p-chloropropyL, l-bromo- 2,4-dichlorohexyl-, 1,3,5-trichlorobutyl-, 2-bromoisobutyl-, chlrocyclopentyl-, 1- chloro-2-bromocyc1ohexyl-, cyanomethyl-, l-chloro-l-cyanoethy1-, B-cyanoethyL, methoxypropy1-, l-ethoxy, 2- chloroethyl-, 1,2-cyano-3-propoXy-butyl-, ethoxypropyl-, phenoxypropy1-, chlorocarbonylmethyl-, chlorocarbonylpropyl-, 1-cyano-3-chlorocarbonylbutyl-, chlorosulphonylethyl-, 1-cyanomethylamino-methyl-, 1-chloro-2-bromoethylaminoethyl-, dimethylaminopropyl-, diethylaminopropyl-, piperidinopropyl-, morpholinoethyland pyrrolidinobutyl-.

Aryl radicals are, for example:

Phenyl-, diphenyl-, napthyl-, phenylene, 2,3,4-chlorophenyl-, 2,3,4-bromophenyl-, 2,3,4-fluorophenyl-, 2,3-dichloro-4-bromophenyl-, 2,4-dichlorophenyl-, 2,4,6-trichlorophenyl-, pentachlorophenyl-, 2,3,4,6-tetrachlorophenyl-, a-chloronaphthyL, 2-chloro-2,5-dicyanophenyl-, 3-cyanophenyl-, 2,5-dicyanophenyl, 3-nitrophenyl-, 2-chloro-4- nitrophenyl-, 4-methoxyphenyl-, 3-ethoxyphenyl-, 2- cyano-3-nitro-4-ethoxyphenyl-, 4-phenoxyphenyl-, 2-chlorocarbonylphenyl-, 3-chlorocarbonylphenyl-, 1-cyano-3,5- dichlorocarbonylphenyl-, 2,4-dichlorocarbonylphenyl-, 4- chlorosulphonylphenyl-, 3 chlorosulphonylphenyl-, chlorosulphonylnapthyl-, 2,3-methylphenyl-, 2,3,4-methylphenyl-, 3 methyl 4-isopropenylphenyl-, 4-is0propylphenyl-, 4-trifiuoromethylphenyl-, 4-[4'-ethylaminobenzyl- 6]-phenyl-, xylyl-, 4-dimethylaminophenyl-3-[Di(fi-chloroethyl)-amino]-phenyl.

Preferred aralkyl radicals are:

Benzyl, p-chlorobenzyl, 2-cyano-5-chlorobenzyl-, p-fiuorobenzyl, 4-chlorosulphonyl-Z-nitrobenzyl, m-chlorobenzyl, m-nitrophenylethyl, naphthylethyl.

Preferred heterocyclic radicals are:

Thiophenyl-(3)-, tetrahydrofury1-(2)-, pyridyl-(2)-, 4- methy1-pyridyl-(2)-, 4,6-dimethyl-pyridyl-(2)-, pyridyl- (4)-, isochinlyl-(1)-, chinolyl-(2)-, 6-chloro-8-cyanochinolyl-(4)-, 6-chloro-7-methy1-8-cyano-chinolyl(4)-, 4- methyl-6-bromo-8-dimethylamino-chinolyl-(2)-, quinolylq y Py y py pyrimidyl-(2,4)-, 2-chloro-pyrazinyl-(3)-, 2-chloro-quinoxalyl (3-, 2 chloro -ethoxy-7-carboxychinoxalyl-(3)-, 2-methyl-4-chloro-triazinyl-(3)-, 2,4-dichloro-s. triazinyl- (6)-, 2-chloro-s.triazinyl-(4,6)-, s.triazinyl-(2,4,6)-, 2- chloro-4-pyrrolidino-s.triazinyl (6)-, 2,4-dipyrrolidino-s.- triazinyl-(6).

Examples of compounds in which R and R are linked via nitrogen, oxygen, sulphur, methine or methylene groups to form a 5- or 6- membered ring are preferably:

Piperazine, 2-methylpiperazine, 2-cyano-5-methylpiperazine, morpholine, thiomorpholine, pyrrolidine, piperidine, tetrahydroquinoline, 5-methoxy-7-cyano-8-chlorotetrahydroquinoline, tetrahydroisoquinoline, 5,7-dichlorotetrahydroisoquinoline, tetrahydroquinoxaline, 2-, 3- or 4- methylpiperidine, 2,4-dimethylpiperidine, Z-methyltetrahydroquinoline.

Besides the formation of the imidochloride grouping, there takes place, dependent upon the conditions of the reaction, an extensive chlorination of the whole molecule, which, under certain conditions, may be accompanied by secondary reactions herein not claimed, such as the splitting off of hydrogen chloride, or aromatisation of ring systems.

There may be used, for example, the following sec- IQ-NII-CAHB 5 amine (German patent specifications Nos. 180,204 and 947,551).

It is, however, to be regarded as definitely surprising that compounds which still carry free hydrogen linked to nitrogen can be subjected to chlorination at elevated temperatures, since the extremely unstable N-chlorine compounds were to be expected as reaction products (cf. Methoden der organischen Chemie (Houben Weyl) 5/3, 4th edition, p. 640). Not only does the simple exchange of hydrogen for chlorine take place, as in the above-mentioned cases at lower temperatures, but, in addition, an imidochloride group is formed according to the invention.

Furthermore, the reaction is all the more surprising as secondary amines which carry a methyl group as second substituent, for example N-methylaniline, are converted by the chlorination under the condition described above into chlorinated carbodiimides.

Compared wtih the chlorinating splitting of tertiary amines and acylamines (Angewandte Chemie 74, 848 (1962)), which results in the same reaction products, the described process oifers the considerable advantage that the formation of the imidochloride grouping takes place already at temperatures starting from 80 C.

The secondary amines employed as starting compounds are obtainable by methods known from the literature.

The process may be explained by the example of the reaction of N-ethylaniline, in which a completely hydrogen-free compound is formed in the presence of a catalyst.

The conditions of chlorination are to be chosen in such a way that initially, at lower temperatures of about 20 to about +60 C., all easily exchangeable hydrogen atoms are substituted by chlorine, optionally under exposure to ultra-violet rays or in other words until at the recited temperature range no further chlorine is consumed. The temperature is then raised, depending on the degree of chlorination desired, to about 70 to about 250 C. to produce the desired formation of the group are valuable products for the preparation of pest control agents, herbicides, dyestuffs, pharmaceutical agents and synthetic resins. Thus, for example, pentachlorophenyl-trichloromethyl-imidochloride is an effective acaricidal agent.

The following examples are given for the purpose of illustrating the invention.

EXAMPLE 1 Hydrogen chloride is passed into a solution of 121 g. N-ethylaniline in 250 cc. chloroform until saturation is achieved. The product is then chlorinated at about 60 C. under ultra-violet light, for about 5 hours. Then the temperature is raised for C. per hour from 60 up to 200 C. As soon as no appreciable evolution of hydrogen chloride can be detected, the temperature is allowed to decrease to about 12 C., 2 g. of iron-III-chloride are added and the chlorination is continued, whilst the temperature is again raised for 20 C. per hour up to 200 C. Chlorine is passed in at this temperature for about 8 hours and the mixture is then subjected to fractional distillation under vacuum. The imidochloride distils over at -170 C. and at 0.15 mm. Hg and solidifies in the receiver to pale yellowish polyhedra of M.P. 129-130 C. The yield of N pentachlorophenyl-trichloromethyl-imidochloride amounts to 360 g.

Analysis.-Calculated for C CI N (molecular weight 429.2) (percent): C, 22.39; Cl, 74.35; N, 3.26. Found (percent): C, 22.64; Cl, 74.0; N, 3.40.

Analog to Example 1 there are obtained:

the N- tetrachloro 3-cyano-phenyl -trichloromethylimidochloride from 3-cyano-N-ethylaniline;

the N-(tetrachloro-4-fluoro-phenyl) pentachloroethylimidochloride from 4-fiuor-N-propylaniline;

the N-(4-isocyanide-dichloro-tetrachloro-phenyl) -trichloromethyl-imidochloride from 4-dimethylamino-N- athylaniline;

the 1,4-bis-(trichloromethyl-imidochloride)-tetrachlorobenzene from N,N'-diethyl-p-phenylenediamine;

the N- [heptachloro-naphthyl- 1) ]trichloromethylimidochloride from l-ethylaminonaphthaline;

the N-[heptachloronaphthyl-( 2) ]-pentachloroethylimidochloride from 2-propylamino-naphthaline.

EXAMPLE 2 158 grams of N-ethylaniline hydrochloride are chlorinated in 250 cc. chloroform under ultra-Violet light for about 8 hours at 40 C. The temperature is then increased for 5 C. per hour from 40 C. up to 90 C. and the chlorination completed at this temperature in about 8 hours. The reaction mixture is distilled under vacuum. Heptachloro-N-phenyl-methyl-imidochloride of B.P. C./1 mm. Hg is obtained.

Analysis.-Calculated for C HCl N (molecular weight 394.8) (percent): C, 24.34; CH, 0.26; Cl, 71.9; N, 3.55. Found (percent): C, 24.15; CH, 0.5; Cl, 72.2; N, 3.41.

Analog to Example 2 there are obtained:

the N-[4-(pentachloroethyl) -dichloro-phenyl]- trichloromethyl-imidochloride from 4-(tetrachloro-ethyl)-N-ethyl-aniline;

the N-[3-trifluoromethyl-trichloro-phenyl] -trichloromethyl-imidochloride from 3-trifluoromethyl-N- ethyl-aniline;

the N-[2-trichloromethyl-dichloro-phenyl]-trichloromethyl-imidochloride from Z-methyI-N-ethylaniline.

EXAMPLE 3 183 parts by Weight of N-benzylaniline are dissolved in 200 parts by weight of chloroform and converted into the hydrochloride by introduction of hydrogen chloride, followed by vigorous chlorination within about 4 hours at temperatures between 20 and 60 C. The chloroform is slowly removed by the chlorine current during this time and the temperature is then raised by 10 C. per hour to 200-220 C. After addition of 3% by weight of FeCl, chlorination is continued at 200 C. The resulting crude imidochloride is purified by recrystallisation from benzine with the addition of 20% by volume of xylene. The compound of the formula 01 C1 C1 G1 I I I l G1 I C1 All C1 C1 is obtained in a yield of 90%. M.P. 273-275 C.

Analysis-Calculated for C CI N (percent): C, 27.83; Cl, 69.67; N, 2.50. Found (percent): C, 28.37; Cl, 69.65; N, 2.67.

Analog to Example 3 there are obtained:

the N- (3 -fiuoro-tetrachloro-phenyl (pentachlorophenyl) -imidochloride from (3-fluorophenyl) benzyl-amino; the N- (heptachloro-naphthyl (pentachloro-phenyl imidochloride.

EXAMPLE 4 298 parts by weight of N-isobutylaniline are dissolved in 200 parts by weight of chloroform and converted into the hydrochloride by passing in hydrogen chloride. The subsequent chlorination is carried out as in Example 3 and purification by recrystallisation from benzine. The compound of the formula is obtained in a yield of 87% of the theoretical. M.P. 135l36 C.

AnaIysis.--Calculated for C CI N (percent): C, 21.07; c1, 76.20; N, 2.73.

EXAMPLE 5 A solution of 151 g. N-[B-hydroxypropyl]-aniline in 300 cc. of chloroform is saturated with hydrogen chloride, 150 grams of thionyl chloride are then added dropwise at 4050 C. The formation of N-[fi-chloropropynaniline hydrochloride, which takes place under vigorous evolution of gas, is completed by continued stirring for two hours.

Chlorine is passed into the suspension of the hydrochloride and the temperature raised within about ten hours from 50 to 200 C. Chlorination is now carried out for six hours at 200 C., the temperature is allowed to fall to 120 C. for the addition of 3 g. of iron-III- chloride and then within about four hours raised again to 200 C. The chlorination is continued at that temperature for about a further 6 hours, in order to complete the exchange of all hydrogen-atoms for chlorine. The reaction mixture is taken up in hot light benzine, the solution treated with activated carbon, and insoluble parts are filtered off from the solution. Upon cooling the N pentachlorophenyl pentachloroethyl imidochloride crystallises out in the form of pale yellow polyhedra of M.P. 132-134 C. After recrystallisation from light benzine the M.P. is 135136 C.

Analysis.Calculated for C CI N (molecular weight 512.1) (percent): C, 21.11; Cl, 76.16; N, 2.74. Found (percent): C, 21.35; C], 75.9; N, 2.98.

The same product is obtained from N-propylaniline.

EXAMPLE 6 Chlorine is passed into the suspension of finely divided hydrochloride of 146 g. diethylamine in 150 cc. trichlorobenzene under ultra-violet light. The temperature is increased to 180 C. within about hours and, as soon as the hydrochloride is dissolved and no appreciable evolution of hydrogen chloride can be observed any longer, the trichlorobenzene is distilled off under the vacuum of a water-jet pump and the temperature raised to 220 C. The residue is then chlorinated for about 12 hours at 220230 C. The imidochloride distills over at 101-105 C./ 0.1 mm. Hg and solidifies in the receiver in the form of colourless crystals of M.P. 7l73 C. The yield of N pentachloroethyl trichloromethyl imidochloride amounts to 520 g.

Analysis.Calculated for C CI N (molecular weight 381.2) (percent): C, 12.61; Cl, 83.72; N, 3.68. Found (percent): C, 12.80; Cl, 82.6; N, 3.87.

Analog to Example 6 there are obtained:

the N-(heptachloro-propyl)-(pentachloroethyl)- imidochloride from bis-(chloro-propyl)- amino;

the bis-(pentachloro-ethyl)imidochloride from ethyl- (chloro-propyl)-amine.

EXAMPLE 7 170 grams of piperidine in 250 cc. chloroform are converted into the hydrochloride by introduction of hydrogen chloride, followed by chlorination for about 16 hours at 45 C., under ultra-violet light. The temperature is then gradually raised for 10 C. per hour up to 200 C. and chlorination continued at 200 C. for about 7 hours. Trichloropyridine of B.P. 95 C./l2 mm. Hg and tetrachloropyridine of B.P. ll0-125 C./12 mm. Hg are obtained by distillation.

Analysis. Calculated for C H Cl N (molecular weight 182.5) (percent): C, 32.92; H, 1.11; Cl, 58.30; N, 7.68. Found: C, 32.81; H, 1.02; Cl, 58.5; N, 7.59.

Calculated for HCl N (molecular weight 216.9) (percent): S, 27.69; H, 0.47; Cl, 65.39; N, 6.46. Found (percent): C, 27.82; H, 0.50; Cl, 65.1; N, 6.60.

Analogous to Example 7 there are obtained:

The pentachloro-quinoline from 1,2,3,4-tetrahydro-quinoline; the trichloro-pyrazine from piperazine.

EXAMPLE 8 193 parts by weight of 2,4-dichloro-6-ethylamino- 1,3,5- triazine are dissolved in 400 parts by weight of chloroform and chlorinated initially at 020 C. After about one hour, the product is exposed to ultra-violet rays and the temperature increased to 60 C. within about 5 hours, whereby the chloroform is gradually driven oil by the flow of chlorine. The chlorination is continued by raising the temperature to about 10 C. per hour up to 200 C.

The product crystallises upon cooling and can be purified, either by distillation or recrystallisation from benzine. The compound of the formula is obtained in a yield of of the theoretical. B.P. 153-160 C./0.3 mm. Hg. M.P., 119-121 C.

AnaIysz's.-Calculated for C Cl N (percent): C, 1824; C1, 64.74; N, 17.02. Found (percent): C, 18.48; Cl, 64.40; N, 17.04.

Analogous to Example 8 there are obtained:

the N-(dichloro-triazinyl)-(pentaihloro-ethyl -imidochloride from dichloro-propylamino-triazine;

the N- trichloro-pyrimidyl (trichloromethyl) -imidochloride from dichloro-ethylamino-pyrimidine;

the N-(dichloro-pyridyl)-(trichloromethyl) -imidochloride from Z-ethyl-amino-pyridine.

EXAMPLE 9 201.5 parts by weight of 2-chloro-4,6-bis-ethylamino- 1,3,5-triazine are dissolved in 400 parts by weight of chloroform and chlorinated as described in Example 8. After removal of the chloroform, 500 parts by weight of trichlorobenzene are added. After termination of the chlorination at 200 C., the trichlorobenzene is distilled off under vacuum and the residue recrystallised from benzine.

9 The yield of N=l-C 01 amounts to 71% of the theoretical. M.P. 116-117 C.

Analysis.-Calculated for C Cl N (percent): C, 17.74; Cl, 67.48; N, 14.78. Found (percent): C, 17.67; Cl, 67.25; N, 14.06.

Analogous to Example 9 there are obtained:

chloroethyl-imidochloride)-triazine from chloro-ethylamino-propylamino-triazine.

EXAMPLE 1O Hydrogen chloride is passed into a solution of 208 parts by Weight 2-ethylamino-3-chloro-quinoxaline in 300 parts -by weight of chloroform until saturation is achieved. The product is then chlorinated at about -60 C. for about 4 hours. The chlorination is slowly removed by the chlorine current and then 300 parts by Weight trichlorbenzene are added. While further introducing chlorine, the temperature is raised for 1 0 C. per hour up to 200 C. Then trichlorobenzene is removed by distillation under reduced pressure and after adding 3 parts by weight of FeCl;,, chlorination is continued for about 5 hours. After cooling and crystallising from gasoline the compound of the formula c1 01 101 o1 =o-c o MP. 140141 C.

Analysis.Calculated for C Cl N (molecular weight 481.5) (percent): C, 24.92; Cl, 66.35; N, 8.72. Found (percent): C, 25.27; C], 65.75; N, 8.94.

Analogous to Example 10 there are obtained:

The N [pentachloro quinoxalyl (2)] pentachloroethyl imidochloride from 2 propylamino 3 -chloroquinoxaline;

the N [6 trichloromethyl trichloro quinoxalyl- (2)] trichlorornethyl imidochloride from 2-ethylamino-3-chloro-6-methyl-quinoxaline;

the 2,3-bis-(trichloromethyl-imidochloride)-dichloroquinoxaline from 2,3-bis-ethylamino-quinoxaline.

EXAMPLE l1 Hydrogen chloride is passed into 330 g. (2 mol) 2- ethyl-amino-benzoic acid in 400 cc. of chloroform until solution is'achieved. 357 g. thionylchloride are dropped in and stirring is continued at 45 C. until the evolution of gas ceases. In this Way the acid chloride of the starting material is obtained, which is chlorinated at a temperature below 60 C. until the development of hydrogen chloride is finished. Chlorination is continued while raising the temperature for 10 C. per hour up to 200 C. When the reaction temperature has reached 200 C. the reaction is finished after chlorinating for further 14 hours.

From the reaction mixture N-(2- chlorocarbonyl-dichlorophenyl) trichloromethyl imidochloride is obtained by distillation as a yellow liquid. B.P. 142-146 C./0.25 mm. Hg.

Analysis.Calculated for C H CL NO (molecular weight 388.3) (percent): C, 27.84; H, 0.52; Cl, 63.92. Found (percent): C, 27.55; H, 0.50; CI, 64.2.

EXAMPLE 12 Chlorine is passed into the suspension of 294 g. hydrochloride of 3-(chloro-ethylamino) 4 chloro-benzotrifluoride in 400 cc. of chloroform at 50 to 60 C. until a clear yellow solution results. The chloroform is distilled oil and the chlorinating temperature is raised for about 10 C. per hour. As soon as 200 C. are reached, chlorination is continued at this temperature until no further hydrogen chloride is evolved. The reaction mixture is distilled under reduced pressure. There are obtained 295 g. of N-(trifluoro-methyl-trichloro-phenyl)- tetrachloro-aza-(1)-propene-(l). B.P. 119 to 124 C./ 0.25 mm. Hg.

Analysis.-Calculated for C HCl- F N (molecular weight 428.3) (percent): C, 25.24; H, 0.23; CI, 57.96; N, 3.27. Found (percent): C, 25.36; H, 0.30; CI, 57.7; N, 4.42.

If the chlorination according to Example 10 is terminated at 200 C. in the presence with 4 g. of iron-III- chloride as a catalyst, there are obtained 315 g. of N- (trifluoro methyl tetrachloro-phenyl)-tetrachloro-aza- (l)-propene-(1) of the formula B.P. 143 to 144 C./0.4 mm. Hg.

Analysis.Calculated for C CI F N (molecular weight 462.8) (percent): C, 23.36; Cl, 61.30; N, 3.03. Found (percent): C, 23.14; Cl, 61.0; N, 3.21.

We claim:

1. A process for the production of chlorine-containing organic nitrogen compounds containing from 1 to 4 imidochloride groupings having the formula which comprises reacting a secondary amine having the formula:

or hydrochlorides of such amines wherein n is a whole number from 1 to 4,

R when taken alone is a member selected from the group consisting of alkyl having 2 to 6 carbon atoms, mono or dinuclear aryl, mono or dinuclear aralkyl, the alkyl group having from 1 to 6 carbon atoms, a 5 or 6 membered heterocyclic radical having from 1 to 3 nitrogen atoms as the only hetero atoms and a 5 or 6 membered heterocyclic radical having 1 to 3 nitrogen atoms as the only hetero atoms containing a fused 4 to 6 membered carbocyclic ring, said members being optionally substituted by halogen, cyano, alkoxy having from 1 to 6 carbon atoms, mono or dinuclear aroxy chlorocarbonyl, sulfur chloride, alkyl having from 1 to 6 carbon atoms, mono or dinuclear aryl, or amino having two radicals attached to the nitrogen, said radicals when taken along being alkyl having from 1 to 6 carbon atoms or mono or dinuclear aryl and said radicals when taken together 11 with the nitrogen to which they are attached being the alkyl 5 or 6 membered heterocyclic ring.

R when taken alone stands for alkyl having from 1 to R and R when taken together are a 5 or 6 membered heterocyclic ring wherein R and R are linked together with methine or methylene groups and wherein such groups may additionally contain up to 2 nitrogen atoms, an oxygen atom or a sulfur atom with the proviso that the heterocyclic atoms are not adjacent one another on the ring, and

R stands for hydrogen or halogen, with chlorine at a temperature between about 20 and +60 C. until all easily exchangeable hydrogen atoms are replaced by chlorine, continuing the chlorination at a temperature between about 70 to 250 C. and isolating the resulting imidochlorides.

2. Process according to claim 1, characterized in that,

12 for the purpose of producing completely hydrogen-free compounds, the final phase of the chlorination is carried out in the presence of halogen-yielding agents selected from the group consisting of A1C1 AlBr FeCl SnCl BF TiCl 3. Process according to claim 1, characterized in that the chlorination of high-melting products is carried out in the presence of inert diluents.

4. Process according to claim 1 wherein R and R are taken together and are a ring selected from the group consisting of piperazine, morpholine, thiomopholine, pyrrolidine, piperidine, tetrahydroquinoline, tetarhydroisoquinoline and tetrahydroquinoxaline.

References Cited Bayer Neth. Appl., Chem. Abstracts, 65:20, 152-3 (1966).

ALEX MAZEL, Primary Examiner R. J. GALLAGHER, Assistant Examiner US Cl. X.R.

331 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3.541.091 natedmlw Inventor) Wilfried Zecher and Horst Ternow and Hans Holtgghn It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shom below:

Column '4, line 10 the right-hand formula should read as follows N H-C H Column t, line 60 the right-hand formula should read as follow:

NHC3 H7 Claim 1, the first formula should read as follows:

Claim 1, the secmd formula should read as follows:

R1 N-C-R H H n 73330 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION page 2 Patent No. sshlogl Dated November 7, 1970 Inventor) Wilfried Zecher and Horst Tarnow and Hans Holtschmi It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 1, line 3 "thiomopholine" should read thiomorpholine Signed and sealed this 26th day of October 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GO'ITSCHALK Attesting Officer Acting Commissioner of Patents 

